JPH02308891A - Light-shielding material - Google Patents
Light-shielding materialInfo
- Publication number
- JPH02308891A JPH02308891A JP12843389A JP12843389A JPH02308891A JP H02308891 A JPH02308891 A JP H02308891A JP 12843389 A JP12843389 A JP 12843389A JP 12843389 A JP12843389 A JP 12843389A JP H02308891 A JPH02308891 A JP H02308891A
- Authority
- JP
- Japan
- Prior art keywords
- light
- acid
- shielding material
- aromatic carboxylic
- metal salt
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000463 material Substances 0.000 title claims abstract description 41
- 150000001875 compounds Chemical class 0.000 claims abstract description 52
- 239000002184 metal Substances 0.000 claims abstract description 26
- 229910052751 metal Inorganic materials 0.000 claims abstract description 26
- 150000003839 salts Chemical class 0.000 claims abstract description 22
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical class OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 19
- YGSDEFSMJLZEOE-UHFFFAOYSA-N Salicylic acid Natural products OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims abstract description 7
- -1 spiropyrans Chemical class 0.000 claims abstract description 6
- 229960004889 salicylic acid Drugs 0.000 claims abstract description 5
- LODHFNUFVRVKTH-ZHACJKMWSA-N 2-hydroxy-n'-[(e)-3-phenylprop-2-enoyl]benzohydrazide Chemical compound OC1=CC=CC=C1C(=O)NNC(=O)\C=C\C1=CC=CC=C1 LODHFNUFVRVKTH-ZHACJKMWSA-N 0.000 claims abstract description 3
- SJJCQDRGABAVBB-UHFFFAOYSA-N 1-hydroxy-2-naphthoic acid Chemical compound C1=CC=CC2=C(O)C(C(=O)O)=CC=C21 SJJCQDRGABAVBB-UHFFFAOYSA-N 0.000 claims abstract 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 claims description 10
- 239000011230 binding agent Substances 0.000 claims description 7
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 6
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- UPHOPMSGKZNELG-UHFFFAOYSA-N 2-hydroxynaphthalene-1-carboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=C(O)C=CC2=C1 UPHOPMSGKZNELG-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- ALKYHXVLJMQRLQ-UHFFFAOYSA-N 3-Hydroxy-2-naphthoate Chemical compound C1=CC=C2C=C(O)C(C(=O)O)=CC2=C1 ALKYHXVLJMQRLQ-UHFFFAOYSA-N 0.000 claims description 3
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 2
- 238000004040 coloring Methods 0.000 abstract description 14
- 150000003751 zinc Chemical class 0.000 abstract description 7
- 150000002500 ions Chemical class 0.000 abstract description 6
- 150000002815 nickel Chemical class 0.000 abstract 1
- 239000011521 glass Substances 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 230000031700 light absorption Effects 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 3
- 238000004042 decolorization Methods 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 238000010494 dissociation reaction Methods 0.000 description 3
- 230000005593 dissociations Effects 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 238000005562 fading Methods 0.000 description 2
- 239000005357 flat glass Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000000123 paper Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- LNETULKMXZVUST-UHFFFAOYSA-N 1-naphthoic acid Chemical class C1=CC=C2C(C(=O)O)=CC=CC2=C1 LNETULKMXZVUST-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- LTEQHMIRAJEJQC-UHFFFAOYSA-N 2-hydroxy-1h-naphthalene-2-carboxylic acid Chemical compound C1=CC=C2C=CC(C(=O)O)(O)CC2=C1 LTEQHMIRAJEJQC-UHFFFAOYSA-N 0.000 description 1
- VHBSECWYEFJRNV-UHFFFAOYSA-N 2-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=CC=C1O.OC(=O)C1=CC=CC=C1O VHBSECWYEFJRNV-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical class [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 101100489867 Mus musculus Got2 gene Proteins 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 1
- 229910001864 baryta Inorganic materials 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Chemical class 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical class [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Chemical class 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000010506 ionic fission reaction Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
- Optical Filters (AREA)
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は、有機フォトクロミック性を示す化合物を用い
た太陽光線等の透過量を調節するための遮光材料に関し
、特に、耐候(光)性、着色安定性を著しく向上せしめ
た耐久性に優れる遮光材料を、提供しようとするもので
ある。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a light-shielding material for adjusting the amount of transmission of sunlight, etc., using a compound exhibiting organic photochromic properties, and in particular, to a light-shielding material that uses a compound exhibiting organic photochromic properties. The object of the present invention is to provide a light-shielding material with excellent durability and significantly improved coloring stability.
〈従来技術〉
フォトクロミズムを示す有機化合物として多く物質が知
られているが、その中で最もよく検討されているのが、
スピロピラン化合物で代表されるスピロフォトクロミッ
ク化合物である。<Prior art> Many substances are known as organic compounds that exhibit photochromism, but the most commonly studied are:
It is a spirophotochromic compound typified by spiropyran compounds.
このような化合物に紫外線を照射すると、ヘテロリック
なイオン解裂を起こして発色し、加熱するか可視光線を
照射すると、消色して元の状態に戻るもので、この現象
は、繰り返し行なわれる。When such a compound is irradiated with ultraviolet rays, it causes heterolic ion dissociation and develops a color, and when heated or irradiated with visible light, the color disappears and returns to its original state. This phenomenon occurs repeatedly. .
光により可逆的に変色する現象をフォトクロミズムと言
われ、この現象を実際に利用し、広く市販されている商
品としては、無機物質であるハロゲン化銀をガラスに分
散した眼鏡レンズが実用化されている。The phenomenon of reversible color change when exposed to light is called photochromism, and a product that actually takes advantage of this phenomenon and is widely available on the market is an eyeglass lens in which silver halide, an inorganic substance, is dispersed in glass. There is.
一方、有機フォトクロミック化合物は、耐光性が十分で
なく、また着色安定性が十分でないため、耐久性を必要
とする遮光材料には不同きなもので、はとんど実用化さ
れるに至っていないものであった。On the other hand, organic photochromic compounds do not have sufficient light resistance or color stability, so they are not suitable for light-shielding materials that require durability, and have hardly been put into practical use. It was something.
有機フォトクロミック化合物の劣化は、光、酸素により
起るものと考えられており、この劣化防止のため、種々
の研究がなされている。Deterioration of organic photochromic compounds is thought to be caused by light and oxygen, and various studies have been conducted to prevent this deterioration.
例えば、酸化防止剤を添加したもの(特開昭58−11
3203 )、紫外線吸収剤を添加したもの(YSP
32t2898他)、−重項酸素失活剤として、ヒンダ
ードアミン等のアミン類、あるいは、ニッケル系金属錯
体等を添加したもの(%開昭58−173181.#開
昭60−42482、特開昭62−252496 )な
どが知られている。For example, those with added antioxidants (Japanese Patent Application Laid-Open No. 58-11
3203), UV absorber added (YSP
32t2898, etc.), - As a heavyt oxygen deactivator, amines such as hindered amines, or nickel-based metal complexes are added (% 173181. 252496) etc. are known.
〈発明が解決しようとする課題〉
しかしながら、前述した改良技術において、酸1化防止
剤を添加した場合、耐光性の向上効果はあまり期待出来
ず、また紫外線吸収剤を添加した場合は、光発色性を低
下せしめたり、有機フォトクロミック化合物の劣化を促
進したりするなどの欠点を有するものであった。又、−
重項酸索失活剤である。アミン類、金属錯体を添加した
ものは、無色透明の樹脂バインダーに分散した場合でも
着色していたり、樹脂バインダーとの相溶性が十分でな
かったりするものである一方、耐光性が末だ十分ではな
いものであった。<Problems to be Solved by the Invention> However, in the above-mentioned improved technology, when an acid monoxide inhibitor is added, it is not expected to have much of an effect on improving light resistance, and when an ultraviolet absorber is added, photochromic However, the organic photochromic compound has drawbacks such as lowering the properties of the organic photochromic compound and promoting deterioration of the organic photochromic compound. Also, -
It is a heavytate acid quencher. Products containing amines or metal complexes may be colored even when dispersed in a colorless and transparent resin binder, or may not have sufficient compatibility with the resin binder, while their light resistance may be poor. It was something that didn't exist.
よって、本発明の目的とするところは、光発色機能を低
下させることなく、高度な耐光性並びに着色安定性に優
れ、かつ耐久性のある有機フォトクロミック化合物を用
いた遮光のための材料な提供しようとするものである。Therefore, it is an object of the present invention to provide a light-shielding material using an organic photochromic compound that has a high degree of light resistance, excellent coloring stability, and durability without reducing the photocoloring function. That is.
く課題を解決するだめの手段〉
すなわち、本発明は
l)へテロリテククイオン解裂性スピロフォトクロミッ
ク化合物と、両性対イオンを形成する芳香族カルボン酸
の2価金属塩とを含有する遮光材料、
2)前項において、前記スピロフォトクロミック化合物
の1モル当量に対して、前記芳香族カルボン酸の2価金
属塩を5モル当量以上含有せしめた遮光材料、
3)前記第1項において、前記芳香族カルボン酸の2価
金属塩がヒドロキシ安息香酸、フタル酸、ヒトロキシナ
フトエ酸、又は、ナフタレンジカルボン酸から選らばれ
た芳香族カルボン酸の2価金属塩である遮光材料、
4)前記第3項の芳香族カルボン酸が、2−ヒドロキシ
安息香酸、l−ヒドロキシ−2−ナフトエ酸、2−ヒド
ロキシ−1−ナフトエ酸、2−ヒドロキシ−3−ナフト
エ酸のいずれかである遮光材料、
5)前記第1〜3項において、芳香族カルボン酸の2価
金属塩が、亜鉛又はニッケルの金属塩である遮光材料、
6)前記第1項の遮光材料を有機バインダー中に溶解も
しくは分散せしめ、支持体上に塗布してなる遮光物品を
提供しようとするものである。Means for Solving the Problems> That is, the present invention provides l) a light-shielding material containing a heterolytic ion-cleavable spirophotochromic compound and a divalent metal salt of an aromatic carboxylic acid forming an amphoteric counterion; 2) In the preceding item, the light-shielding material contains 5 or more molar equivalents of the divalent metal salt of the aromatic carboxylic acid per 1 molar equivalent of the spirophotochromic compound; A light-shielding material in which the divalent metal salt of an acid is a divalent metal salt of an aromatic carboxylic acid selected from hydroxybenzoic acid, phthalic acid, hydroxynaphthoic acid, or naphthalene dicarboxylic acid, 4) the aromatic aroma of item 3 above; 5) a light-shielding material in which the group carboxylic acid is any one of 2-hydroxybenzoic acid, l-hydroxy-2-naphthoic acid, 2-hydroxy-1-naphthoic acid, and 2-hydroxy-3-naphthoic acid; 5) the first light-shielding material; 3) A light-shielding material in which the divalent metal salt of an aromatic carboxylic acid is a metal salt of zinc or nickel; 6) The light-shielding material of item 1 above is dissolved or dispersed in an organic binder, and the divalent metal salt of an aromatic carboxylic acid is disposed on a support. The purpose is to provide a light-shielding article formed by applying the same.
まず、本発明に係る遮光材料に使用するヘテロリプツク
イオン解裂性スピロフォトクロミック化合物の代表的な
ものは、下記一般式で表わすことが出来るものである。First, a typical heteroliptic ion-cleavable spirophotochromic compound used in the light shielding material according to the present invention can be represented by the following general formula.
より具体的には、上記一般式〇)において、XがCM、
Yが0原子であるスピロピラン系化合物、xがca、y
がS原子であるスピロチオビラン系化合物、XがN原子
、YがO原子であるスピロオキサジン系化合物、スピロ
ナフトオキサジン系化合物が例示出来る。More specifically, in the above general formula 〇), X is CM,
Spiropyran compound where Y is 0 atom, x is ca, y
Examples include spirothiobilane compounds where X is an S atom, spirooxazine compounds where X is an N atom and Y is an O atom, and spironaphthoxazine compounds.
なお、一般式〔I〕において、aIA及び環Bで示めさ
れる芳香環の置換基としては、アルキル基、アルコキシ
基、アルコキシカルボニル基又ハアルコキシスルホニル
基、アルキルフェノール基、ハロゲン原子、ニトロ基が
例示出来る。In the general formula [I], the substituents on the aromatic ring represented by aIA and ring B include an alkyl group, an alkoxy group, an alkoxycarbonyl group, a haalkoxysulfonyl group, an alkylphenol group, a halogen atom, and a nitro group. I can give an example.
上述したスピロフォトクロミック化合物においては、そ
の構造及び置換基の種類により、発色状態での色相、す
なわち光吸収域が異なるものであり、遮光の目的に合せ
て選択もしくは組み合せて使用することが必要である。The above-mentioned spirophotochromic compounds have different hues in the coloring state, that is, light absorption ranges, depending on their structures and types of substituents, and it is necessary to select or use them in combination according to the purpose of light shielding. .
これらスピロフォトクロック化合物のうちでもスヒロオ
キサジン系、スピロナフトオキサジン系化合物は、耐光
性でスピロピラン系化合物よす優れるものであり、又ス
ピロチオビラン系化合物においては、発色波長か70O
Im以上に高い吸収特性を有するため、熱線吸収を含め
た遮光用途に適するものである。Among these spirophotoclock compounds, spirooxazine and spironaphthoxazine compounds are superior in light resistance to spiropyran compounds, and spirothiobilane compounds have a coloring wavelength of 70O
Since it has higher absorption characteristics than Im, it is suitable for light shielding applications including heat ray absorption.
これらスピロフォトクロック化合物は、紫外線を照射す
ると以下のようなヘテロリテックィオン解裂性を示して
、
スピロピラン系化合物及びスピロオキサジン系化合物の
場合:
無色状態 発色状態スピロチオピラ
ン系化合物の場合:
のように発色するものであり、可視光の照射又は熱によ
って消色するものである。When these spirophotoclock compounds are irradiated with ultraviolet rays, they show the following heterolytic cleavage properties: In the case of spiropyran compounds and spirooxazine compounds: Colorless state In the case of spirothiopyran compounds: Color development The color is erased by visible light irradiation or heat.
これら、スピロフォトクロミック化合物はそれぞれ単独
でもしくは混合して使用することによって、発色状態の
色相並びに吸光量を任意にコントロールすることが出来
、400nm〜700nm あるいは700nm以上の
範囲の可視光、近赤外線を遮光することが出来るもので
ある。By using these spirophotochromic compounds alone or in combination, the hue of the coloring state and the amount of light absorption can be controlled arbitrarily, and they block visible light and near infrared rays in the range of 400 nm to 700 nm or 700 nm or more. It is something that can be done.
なお、本発明に係るスピロフォートクロミック化合物と
しては、上述の各化合物以外に、それら化合物の二量体
、三量体など、あるいは上述化合物に重合材ビニル基を
導入してそれを重合せしめた重合物なども同様使用出来
るものである。In addition to the above-mentioned compounds, spirofortchromic compounds according to the present invention include dimers, trimers, etc. of these compounds, and polymers obtained by introducing a polymeric vinyl group into the above-mentioned compounds and polymerizing them. Objects can also be used in the same way.
一方の成分である両性対イオンを形成する芳香族カルボ
ン酸の2価金属塩としては、分子中にヒドロキンル基と
カルボキシル基又は2つのカルボキシル基を有する芳香
族酸の2価金属塩であり、具体的には、ヒドロキシ安息
香酸、フタル酸、ヒドロキンナフトエ酸、ナフタレンジ
カルボン酸等の亜鉛、ニッケル、銅、コバルト等の金属
塩が例示出来る。The divalent metal salt of an aromatic carboxylic acid that forms the amphoteric counterion that is one of the components is a divalent metal salt of an aromatic acid that has a hydroquine group and a carboxyl group or two carboxyl groups in the molecule. Specific examples include metal salts of zinc, nickel, copper, cobalt, etc., such as hydroxybenzoic acid, phthalic acid, hydroquinaphthoic acid, and naphthalene dicarboxylic acid.
ほかでも2−ヒドロキシ安息香酸(サリチル酸)、1−
ヒト10キシ−2−ナフトエ酸、2−ヒドロキシ−1−
ナフトエ酸、2−ヒ□ドロキシー3−ナフトエ酸の2価
金属塩が好ましく、2価の金属のうちでも亜鉛、ニッケ
ルの金属塩が特に好ましいものである。Among others, 2-hydroxybenzoic acid (salicylic acid), 1-
Human 10x-2-naphthoic acid, 2-hydroxy-1-
Divalent metal salts of naphthoic acid and 2-hydroxy-3-naphthoic acid are preferred, and among the divalent metals, metal salts of zinc and nickel are particularly preferred.
は、紫外線の照射で一世飽和発色濃度に達した後、更に
光照射を続けると、退色する挙動を示すもので、発色状
態での安定性、耐光性が著しく低いものであるが、本発
明で特定する化合物を組み合せた場合は、送光挙動を全
く示さfいかあるいは顕著な退色抑制効果を示すもので
ある。又、熱消色挙動においても、スピロフォトクロミ
ック化合物単独では、急速な消色挙動を示めすが、本発
明の系においては、着色安定性が極めて高く、弱い室内
光程度では容易に消色しないものである。After reaching a saturated color density by irradiation with ultraviolet rays, it exhibits the behavior of fading when irradiated with light, and its stability and light resistance in the coloring state are extremely low. When the specified compounds are combined, either no light transmission behavior is exhibited or a remarkable fading inhibiting effect is exhibited. In addition, in terms of thermal decolorization behavior, spirophotochromic compounds alone exhibit rapid decolorization behavior, but the system of the present invention has extremely high coloring stability and does not easily decolorize under weak indoor light. It is.
スピロフォトクロミック化合物の発色状態、すなわちヘ
テロリテックィオン解裂状態において、両性対イオンを
形成する芳香族カルボン酸の金属塩は、イオン解裂状態
の安定化に寄与しているものと考えられる。サリチル酸
の亜鉛塩の場合な例として示めせば、
光l
のようになると考えられる。In the colored state of the spirophotochromic compound, that is, in the heterolytic ion dissociation state, the metal salt of the aromatic carboxylic acid that forms the amphoteric counterion is considered to contribute to stabilizing the ionic dissociation state. For example, in the case of zinc salt of salicylic acid, it would be like light l.
なお、本発明に係る遮光材料において、前記スピロフォ
トクロミック化合物と、前記芳香族カルボン酸の金属塩
との混合比率は、前者1モル当量に対して、後者を5モ
ル半量以上、より好ましくは10モル当量以上にするこ
とによって、耐光性、着色安定性をより高く維持するこ
とが出来るものである。In addition, in the light-shielding material according to the present invention, the mixing ratio of the spirophotochromic compound and the metal salt of aromatic carboxylic acid is such that the latter is 5 and a half moles or more, more preferably 10 moles or more, per 1 mole equivalent of the former. By using an equivalent amount or more, light resistance and coloring stability can be maintained even higher.
以上説明した2種の化合物を組み合せて、目的とする遮
光材料とする場合は、適当な溶剤及び有機バインタフ−
中に溶解もしくは分散せしめてコーティング剤等を作成
し、適当な支持体上に塗布するかもしくは支持体を用い
ることなく、フィルム化して、遮光材料を得ることが出
来る。When combining the two types of compounds described above to form the desired light-shielding material, use an appropriate solvent and organic binder.
A light-shielding material can be obtained by dissolving or dispersing the light-shielding material into a coating agent, etc., and coating it on a suitable support or forming a film without using a support.
本発明で使用する有機バインダーとしては、前記化合物
との相溶性が良いもので、光学的に透明であり、かつ皮
膜形成能に優れるものであれば使用出来、具体的には、
アクリル系、スチレン系、酢酸ビニル、ポリブチラール
、セルロース系、塩化ビニル、塩化ビニリデン、ポリオ
レフィン系の重合体も、しくは共重合体、ポリウレタン
樹脂、ボリカーボI−ネート樹脂、エポキシ樹脂、フェ
ノキク樹脂、ポリエステル樹脂などが例示出来る。The organic binder used in the present invention may be one that has good compatibility with the above-mentioned compounds, is optically transparent, and has excellent film-forming ability; specifically,
Acrylic, styrene, vinyl acetate, polybutyral, cellulose, vinyl chloride, vinylidene chloride, polyolefin polymers or copolymers, polyurethane resin, polycarbonate resin, epoxy resin, phenolic resin, polyester Examples include resin.
また、溶解すべき有機溶剤としては、メタノール、エタ
ノール、イソプロピルアルコールナトのアルコール類、
アセトン、メチルエチルケトン、シクロヘキサノンなど
のケトン類、エチルエーテル、ジオキサン、テトラヒド
ロフランなどのエーテル類、酢酸エチル、酢酸n−ブチ
ルなどのエステル類、更にベンゼン、クロルベンゼン、
トルエン、キシレン、n−ヘキサン、シクロヘキサン、
アセトニトリル、ジメチルホルムアミド、ジメチルスル
ホキッド、クロロキルム、塩化メチレン、1.2−ジク
ロルエタン、トリクロロエチレン、四塩化炭素など及び
これらの混合物を用いることができる。In addition, the organic solvents to be dissolved include alcohols such as methanol, ethanol, and isopropyl alcohol;
Ketones such as acetone, methyl ethyl ketone and cyclohexanone, ethers such as ethyl ether, dioxane and tetrahydrofuran, esters such as ethyl acetate and n-butyl acetate, as well as benzene, chlorobenzene,
Toluene, xylene, n-hexane, cyclohexane,
Acetonitrile, dimethylformamide, dimethylsulfokide, chlorocyrm, methylene chloride, 1,2-dichloroethane, trichloroethylene, carbon tetrachloride, and mixtures thereof can be used.
テート、ポリカーボネートのプラスチック材料、通常の
紙、バライタ紙、ガラス、金属等がある。There are plastic materials such as tate, polycarbonate, regular paper, baryta paper, glass, metal, etc.
以上のバインダー、有機溶剤中に本発明に係るスピロフ
ォトクロミック材料、前記芳香族カルボン酸の金属塩を
分散せしめ、前述支持体上に塗布して乾燥せしめるか、
あるいは支持体なしにフィルム状にすることによって遮
光材料が得られるが、その他必要に応じて、従来より使
用されている酸化防止剤、紫外線吸収剤、更には、−1
項酸素失活剤などを添加することが出来るものである。The spirophotochromic material according to the present invention and the metal salt of the aromatic carboxylic acid are dispersed in the binder and organic solvent described above, and the mixture is coated on the support and dried, or
Alternatively, a light-shielding material can be obtained by making it into a film without a support, but if necessary, conventionally used antioxidants, ultraviolet absorbers, and -1
It is possible to add an oxygen deactivator or the like.
本発明に係る遮光材料は、スピロフォトクロミック化合
物の種類の選択あるいは発色状態での吸光特性の異なる
ものを組み合せることによって、可視光領域はもとより
近赤外領域の光を遮光するなどの調光が可能になる。な
お、本発明の遮光材料は、発色状態での安定性に優れる
ため、自然可視光の照射程度では容易に消色しないもの
であるが、消色のためには可視光照射手段以外に加熱手
段、或いはエレクトロクロック性を付与するための電気
化学的な酸化、還元反応を制御する手段を講じることに
よって任意に消色させることは可能である。The light-shielding material according to the present invention can be light-modulated by blocking not only visible light but also light in the near-infrared region by selecting the type of spirophotochromic compound or by combining spirophotochromic compounds with different light absorption characteristics in the colored state. It becomes possible. Note that the light-shielding material of the present invention has excellent stability in a colored state, and therefore does not easily discolor by irradiation with natural visible light. Alternatively, it is possible to arbitrarily erase the color by taking measures to control electrochemical oxidation and reduction reactions to impart electroclockability.
〈実施例〉
実施例1
で示めされるスピロピラン化合物3.59 (0,01
モル)、サリチル酸25g(0,t5モル)及びポリメ
チルメタクリレート(住友化学社製スミペックスBMR
)100 gに、酢酸ブチル、トルエン、ブタノールの
1:l:1の混合溶剤225gを加えてコーティング剤
を作成し、光学研磨したガラス板上に塗布・乾燥せしめ
、遮光材料lを得た。<Example> Spiropyran compound shown in Example 1 3.59 (0,01
mol), salicylic acid 25g (0,t5 mol) and polymethyl methacrylate (SumiPex BMR manufactured by Sumitomo Chemical Co., Ltd.
) and 225 g of a 1:1:1 mixed solvent of butyl acetate, toluene, and butanol were added to prepare a coating agent, which was applied onto an optically polished glass plate and dried to obtain a light-shielding material 1.
実施例2゜
実施例1と同じスピロピラン化合物に、l−ヒドロキシ
−2−ナフトエ酸の亜鉛塩を同じモル比率で混合し、同
様コーティング剤を作成し、ガラス板上に塗布・乾燥せ
しめて遮光材料2を得た。Example 2 The same spiropyran compound as in Example 1 was mixed with zinc salt of l-hydroxy-2-naphthoic acid in the same molar ratio to prepare a coating agent in the same manner as in Example 1, and the coating agent was applied and dried on a glass plate to produce a light-shielding material. I got 2.
実施例3〜4
で示めされるスピロオキサジン化合物3.31 (0,
01モル)に、l−ヒドロキシ−2−ナフトエ酸の亜鉛
塩3310.15モル)(実施例3)、及び2−ヒドロ
キX/−3−ナフトエ酸の亜鉛塩33g(0,15モル
)(実施例4)をそれぞれ混合し、実施例1と同様にコ
ーティング剤を作成し、ガラス板上に塗布・乾燥せしめ
、遮光材料3及び4を作成する。Spirooxazine compounds shown in Examples 3-4 3.31 (0,
01 mol), 3310.15 mol) of the zinc salt of l-hydroxy-2-naphthoic acid (Example 3), and 33 g (0.15 mol) of the zinc salt of 2-hydroxy-2-naphthoic acid (example 3). Example 4) were mixed respectively to prepare a coating agent in the same manner as in Example 1, and the coating agent was applied onto a glass plate and dried to prepare light shielding materials 3 and 4.
比較例1〜2
実施例1及び3のコーティング剤において、芳香族カル
ボン酸の亜鉛塩を添加しなかったコーティング剤を使用
し、ガラス板上に塗布・乾燥せしめ、比較遮光材料1及
び2を作成した。Comparative Examples 1 to 2 Comparative light-shielding materials 1 and 2 were created by using the coating agents of Examples 1 and 3 to which the zinc salt of aromatic carboxylic acid was not added, and applying and drying them on a glass plate. did.
実施例1〜4及び比較例1〜2で得た遮光材料を用い、
スガ試験機製のカーボンアーク灯を備えり
たウエザーメーか−で紫外線を150時間暴露し、各化
合物の飽和発色における最大吸収波長における光学濃度
に対する残存光学濃度を分光光度計を用いて測定し、耐
光性を評価した。Using the light shielding materials obtained in Examples 1 to 4 and Comparative Examples 1 to 2,
We exposed each compound to ultraviolet light for 150 hours using a weather camera equipped with a carbon arc lamp manufactured by Suga Test Instruments, and measured the residual optical density relative to the optical density at the maximum absorption wavelength for saturated color development using a spectrophotometer. was evaluated.
一方、暗所における着色力の安定性についても評価する
ため、暗所に48時間放置したときの残存光学濃度を同
様にして測定した。評価結果は、表−1に示す。On the other hand, in order to evaluate the stability of the tinting strength in the dark, the residual optical density was measured in the same manner when the sample was left in the dark for 48 hours. The evaluation results are shown in Table-1.
表−1
実施例5〜7
実施例3で使用したスピロオキサジン化合物の1モル当
量に対して、l−ヒドロキシ−2−ナフトエ酸の亜鉛塩
の混合比率を、5モル当量(実施例5)、10モル当量
(実施例6)、20モル当量(実施例7)にそれぞれ変
化せしめ、同様にコーティング剤を作成し、ガラス板上
に塗布・乾燥して、遮光材料5〜7を得た。Table-1 Examples 5 to 7 With respect to 1 molar equivalent of the spirooxazine compound used in Example 3, the mixing ratio of zinc salt of l-hydroxy-2-naphthoic acid was 5 molar equivalent (Example 5), The amount was changed to 10 molar equivalents (Example 6) and 20 molar equivalents (Example 7), coating agents were prepared in the same manner, and coated on a glass plate and dried to obtain light shielding materials 5 to 7.
評価試験2
評価試験lと同様に実施例5〜7及び比較例2の遮光材
料について耐光性及び着色安定性を調べ、その結果を表
−2に示す。Evaluation Test 2 Similarly to Evaluation Test 1, the light resistance and coloring stability of the light shielding materials of Examples 5 to 7 and Comparative Example 2 were investigated, and the results are shown in Table 2.
表−2
く効果〉
以上、実施例で具体的に示めしたとおり、本発明に係る
遮光材料においては、スピロフォトクロミック化合物単
独の場合に比べ、耐光性並びに着色安定性が著しく改善
されているものである。Table 2 Effects> As specifically shown in the examples above, the light-shielding material according to the present invention has significantly improved light resistance and coloring stability compared to the case of using a spirophotochromic compound alone. It is.
又、耐光性並びに着色安定性の同上については、スピロ
フォトクロミック化合物と、両性対イオンを形成する芳
香族カルボン酸の混合比率が大きく影響するもので、前
者に対して、後者を少なくとも5モル当量以上、より好
ましくは10モル当量以上にすることが耐久性に優れる
遮光材料を得る上で必要なことがわかる。In addition, the light resistance and coloring stability mentioned above are greatly influenced by the mixing ratio of the spirophotochromic compound and the aromatic carboxylic acid that forms the amphoteric counterion, and the latter is at least 5 molar equivalents of the former. , more preferably 10 molar equivalents or more is necessary in order to obtain a light-shielding material with excellent durability.
よって、本発明に従えば、使用する化合物の種類を選定
することによって発色状態での光吸収特性を可視光全領
域から、近赤外付近までに調整することが出来るため、
窓カラス等の建材用或いは自動車等の乗物の窓ガラス等
の光透過制御のための耐久性に優れた遮光材料として使
用することが出来るものである。又、発色状態が極めて
安定であり、室内光等の可視光では消色が容易でないこ
とから、強制的な消色手段、例えば熱的手段もしくはエ
レクトロクロミック性を付与するなどの電気化学的手段
を併用することによって、発色、消色を人為的に制御す
ることも出来るものである。Therefore, according to the present invention, by selecting the type of compound used, the light absorption characteristics in the coloring state can be adjusted from the entire visible light range to near the near infrared.
It can be used as a highly durable light-shielding material for building materials such as window glass, or for controlling light transmission in window glass for vehicles such as automobiles. In addition, since the coloring state is extremely stable and it is not easy to erase the color with visible light such as indoor light, forced color erasing means, such as thermal means or electrochemical means such as imparting electrochromic properties, are required. By using them together, it is also possible to artificially control color development and decolorization.
#fc+f−出顔人 サカタインクス株式会社(外3
名)#fc+f-appearance person Sakata Inx Co., Ltd. (outside 3
given name)
Claims (1)
ク化合物と、両性対イオンを形成する芳香族カルボン酸
の2価金属塩とを含有することを特徴とする遮光材料。 2)請求項第1項において、前記スピロフォトクロミッ
ク化合物の1モル当量に対して、前記芳香族カルボン酸
の2価金属塩を5モル当量以上含有せしめた遮光材料。 3)請求項第1項において、前記芳香族カルボン酸の2
価金属塩がヒドロキシ安息香酸、フタル酸、ヒトロキシ
ナフトエ酸、又は、ナフタレンジカルボン酸から選ばれ
た芳香族カルボン酸の2価金属塩である遮光材料。 4)請求項第3項の芳香族カルボン酸が、2−ヒドロキ
シ安息香酸、1−ヒドロキシ−2−ナフトエ酸、2−ヒ
ドロキシ−1−ナフトエ酸、2−ヒドロキシ−3−ナフ
トエ酸のいずれかである遮光材料。 5)請求項第1〜3項において、芳香族カルボン酸の2
価金属塩が、亜鉛又はニッケルの金属塩である遮光材料
。 6)請求項第1項の遮光材料を有機バインダー中に溶解
もしくは分散せしめ、支持体上に塗布してなる遮光物品
。[Scope of Claims] 1) A light-shielding material characterized by containing a heterolytic ion-cleavable spirophotochromic compound and a divalent metal salt of an aromatic carboxylic acid that forms an amphoteric counterion. 2) The light-shielding material according to claim 1, wherein the divalent metal salt of the aromatic carboxylic acid is contained in an amount of 5 molar equivalents or more based on 1 molar equivalent of the spirophotochromic compound. 3) In claim 1, 2 of the aromatic carboxylic acid
1. A light-shielding material, wherein the valent metal salt is a divalent metal salt of an aromatic carboxylic acid selected from hydroxybenzoic acid, phthalic acid, hydroxynaphthoic acid, or naphthalene dicarboxylic acid. 4) The aromatic carboxylic acid of claim 3 is any one of 2-hydroxybenzoic acid, 1-hydroxy-2-naphthoic acid, 2-hydroxy-1-naphthoic acid, and 2-hydroxy-3-naphthoic acid. A certain light-shielding material. 5) In claims 1 to 3, 2 of the aromatic carboxylic acids
A light-shielding material whose valent metal salt is a zinc or nickel metal salt. 6) A light-shielding article obtained by dissolving or dispersing the light-shielding material according to claim 1 in an organic binder and coating it on a support.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP12843389A JPH0796678B2 (en) | 1989-05-22 | 1989-05-22 | Shading material |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP12843389A JPH0796678B2 (en) | 1989-05-22 | 1989-05-22 | Shading material |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH02308891A true JPH02308891A (en) | 1990-12-21 |
JPH0796678B2 JPH0796678B2 (en) | 1995-10-18 |
Family
ID=14984627
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP12843389A Expired - Lifetime JPH0796678B2 (en) | 1989-05-22 | 1989-05-22 | Shading material |
Country Status (1)
Country | Link |
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JP (1) | JPH0796678B2 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR101037858B1 (en) * | 2007-08-14 | 2011-05-31 | 주식회사 엘지화학 | Photochromic composition and product produced by the same |
JP2011519420A (en) * | 2008-04-16 | 2011-07-07 | ビーエーエスエフ ソシエタス・ヨーロピア | Optimized time / temperature indicator |
-
1989
- 1989-05-22 JP JP12843389A patent/JPH0796678B2/en not_active Expired - Lifetime
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR101037858B1 (en) * | 2007-08-14 | 2011-05-31 | 주식회사 엘지화학 | Photochromic composition and product produced by the same |
JP2011519420A (en) * | 2008-04-16 | 2011-07-07 | ビーエーエスエフ ソシエタス・ヨーロピア | Optimized time / temperature indicator |
Also Published As
Publication number | Publication date |
---|---|
JPH0796678B2 (en) | 1995-10-18 |
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